We study two-dimensional direction of arrival (2D-DOA) estimation problem of monostatic MIMO radar with the receiving array which consists of electromagnetic vector sensors (EMVSs). The proposed angle estimation algorithm can be applied to the arbitrary and unknown array configuration, which can be summarized as follows. Firstly, EMVSs in the receiver of a monostatic MIMO radar are used to measure all six electromagnetic-field components of an incident wavefield. The vector sensor array with the six unknown electromagnetic-field components is divided into six spatially identical subarrays. Secondly, ESPRIT is utilized to estimate the rotational invariant factors (RIFs). Parts of the RIFs are picked up to restore the source’s electromagnetic-field vector. Last, a vector cross product operation is performed between electric field and magnetic field to obtain the Pointing vector, which can offer the 2D-DOA estimation. Prior knowledge of array elements’ positions and angle searching procedure are not necessary for the proposed 2D-DOA estimation method. Simulation results prove the validity of the proposed method.